CN103608407B - High refraction composition - Google Patents
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- CN103608407B CN103608407B CN201280029922.4A CN201280029922A CN103608407B CN 103608407 B CN103608407 B CN 103608407B CN 201280029922 A CN201280029922 A CN 201280029922A CN 103608407 B CN103608407 B CN 103608407B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Abstract
The application relates to a kind of high refraction composition. Transparency, moisture resistance, heat resistance, resistance to water, weatherability, light resistance and the durability of the application's compositions display excellence, and can form the high refraction film with high index of refraction. Described composition is in process or show hardly afterwards outgas, and can adopt solution coat method to apply, therefore can be effectively for multiple electro-optical device.
Description
Technical field
The application relates to a kind of high refraction composition.
Background technology
High refractiveness resin can have anti-reflective effect, light scattering effect or light extraction effect for needsOptical element. For example, high refractiveness resin can be for plastic optical lens, for video disc recordingHigh-precision lenses, prism, optical fiber, optical waveguide, optical adhesive, packaging optical semiconductor or functionMaterial, for example, antireflective coating, light-diffusing films, visual angle increase film; Brightness improves film or optical filter, itsCan be applied to PDP (plasma display) or LCD (liquid crystal display). In addition high refractiveness tree,Fat can be for preventing the deteriorated additive of plasticity, for the additive of cosmetics or for the window of vehicleGlass etc.
As the method for the high refractiveness resin of preparation, the method (patent documentation of the resin of known introducing based on sulphur1), use the method (patent documentation 2) of the resin of introducing halogen and method (the patent literary composition of use metal oxideOffer 3 to 5).
But according to conventional method, attainable refractive index is limited, and heat resistance, weatherability etc.Decline. In addition, even, after curing schedule, under hot conditions, can continue to occur outgas phenomenon, thisIn the time of fabricate devices, cause problem. Although known use metal oxide is as giving high index of refractionThe method of material, if when the amount of metal oxide exceedes certain level, it assembles in cured product,Cause light scattering and deteriorated transparency seriously. In addition, can not keep the stable of metal oxide particleDisperse, and particle trend is sunk.
[prior art document]
[patent documentation]
No. 2006-307200th, (patent documentation 1) Japanese Patent Laid-Open Publication
No. 2001-011109th, (patent documentation 2) Japanese Patent Laid-Open Publication
No. 2008-280202nd, (patent documentation 3) Japanese Patent Laid-Open Publication
No. 2007-084374th, (patent documentation 4) Japanese Patent Laid-Open Publication
No. 2009-137774th, (patent documentation 5) Japanese Patent Laid-Open Publication
Summary of the invention
Technical problem
The application provides has high refrangible composition.
Technical scheme
The example in this application with high refrangible composition can comprise silicones or its precursor, andOrgano-metallic compound or its condensation product. Term " silicones " in this manual can be illustrated in its boneIn frame, comprise the compound that is selected from least two kinds of siloxane units in siloxane unit M, D, T and Q.
In this manual, can represent conventionally can be by chemical formula (R for term " M unit "3SiO1/2) representSo-called simple function siloxane unit. Term " D unit " can represent conventionally can be by chemical formula(R2SiO2/2) represent so-called difunctional siloxane unit. Term " T unit " can represent conventionally can be byChemical formula (RSiO3/2) represent so-called trifunctional siloxane unit. Term " Q unit " can represent conventionallyCan be by chemical formula (SiO4/2) represent four functional silicone unit. At this, each R is for being directly connected toSubstituting group on silicon atom, and represent independently: for example, hydrogen, hydroxyl, epoxy radicals, acryloyl group (acrylGroup), methacryl (methacrylgroup), acryloxy (acryloylgroup), methyl-propAlkene acyloxy (methacryloylgroup), NCO, alkoxyl or monovalence alkyl.
Term " has high refrangible composition " and can represent that refractive index is, for example, more than 1.50,1.55Above, more than 1.60, more than 1.65, more than 1.7, or more than 1.8 composition, or after solidifyingThere is the composition of the refractive index in above-mentioned scope arbitrarily. Described refractive index is according to described belowMethod is used UV-VIS spectrometer to obtain the photo measure of wavelength 450nm.
Described composition comprises silicones or can form the precursor of described silicones, and organic metalCompound or its condensation product. In exemplary embodiment, described composition is cured and becomes toolThere is the silicon hybridization film of high index of refraction. Work in-process, described composition can not cause and be separated, and formThere is the high refractiveness film of excellent transparency. In addition, described composition or high refractiveness film have and compriseThe excellent performance of heat resistance, weatherability and mechanical strength etc., and can not in process or afterwardsCause outgas phenomenon. In addition, even if desired by other deposition of material or be laminated to described high refractiveness filmUpper, this high refractiveness film can be not deteriorated, in fabricate devices process, is therefore favourable.
Described composition comprises silicones and maybe can form the precursor of silicones. For example, described silicones canRepresent with the average group accepted way of doing sth 1 by Chemical formula 1.
[Chemical formula 1]
(R3SiO1/2)a(R2SiO2/2)b(RSiO3/2)c(SiO4/2)d(XO1/2)e
In Chemical formula 1, each R is the substituting group being connected on silicon atom, and represent independently hydrogen,Alkyl or aryl, X represents hydrogen atom or alkyl, a+b+c+d+e is 1, and a 0 to 0.6, b is0 to 0.97, c is 0 to 0.8, d to be 0 to 0.4, e to be 0 or positive number. If described silicones is for belowBy the crosslinked resin of describing,, in Chemical formula 1, c and d cannot be 0 simultaneously.
In the present invention, described silicones can be represented by an a certain average group accepted way of doing sth. Naturally, when describedWhen composition comprises single silicones, described silicones can be represented by an average group accepted way of doing sth, and work as instituteWhen stating composition and comprising multiple silicones, the average composition of this multiple silicones can be by average group accepted way of doing sth tableShow.
In Chemical formula 1, each R is the substituting group being connected on silicon atom, can be mutually the same or notWith, and represent independently hydrogen, alkyl or aryl. When if desired, described alkyl or aryl can be by oneIndividual above substituting group replaces. Can comprise for the substituting group of substituted alkyl or aryl: halogen,Hydroxyl, epoxy radicals, acryloyl group, methacryl, acryloxy, methacryloxy,NCO, sulfydryl, alkoxyl or monovalence alkyl. In an exemplary embodiment, ifAlkyl or aryl comprises more than one substituting group, and can not comprise can thermosetting or can light for described substituting groupCuring substituting group, for example, epoxy radicals, hydroxyl, acryloyl group, methacryl, acryloyl-oxyBase, methacryloxy, NCO or alkyl.
Unless the article pointed out up and down, term " alkoxyl " can represent to have 1 to 20 carbon atom, 1To 16 carbon atoms, 1 to 12 carbon atom, the alkane of 1 to 8 carbon atom or 1 to 4 carbon atomOxygen base. Described alkoxyl can be the alkoxyl of straight chain, side chain or ring-type, and can be optionallyReplaced by more than one substituting group.
Term " monovalence alkyl " can represent from the compound of carbon and hydrogen composition or carbon and hydrogen composition and whereinThe monovalence residue that the compound that at least one hydrogen atom is replaced by a certain substituting group obtains. For example, described oneValency alkyl can have 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom, 1 to8 carbon atoms or 1 to 4 carbon atom. For example, described monovalence alkyl can comprise alkyl, thiazolinyl or virtueBase.
Unless the article pointed out up and down, term " alkyl " can represent to have 1 to 20 carbon atom, 1 to16 carbon atoms, 1 to 12 carbon atom, the alkyl of 1 to 8 carbon atom or 1 to 4 carbon atom.Described alkyl can be the alkyl of straight chain, side chain or ring-type, and can be optionally by more than oneSubstituting group replace.
In addition, unless the article pointed out up and down, term " thiazolinyl " can represent to have 2 to 20 carbon atoms,2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atomsThiazolinyl. Described thiazolinyl can be the thiazolinyl of straight chain, side chain or ring-type, and can be optionally by oneIndividual above substituting group replaces.
Term " aryl " can represent from have that phenyl ring or plural phenyl ring connect or the structure that condenses orThe monovalence residue that its derivative obtains. Term " aryl " not only can comprise the functional group of so-called aryl,Also comprise so-called aralkyl or aryl alkyl. For example, described aryl can be former for having 6 to 25 carbonThe aryl of son or 6 to 21 carbon atoms, and can comprise phenyl, dichlorophenyl, chlorphenyl, phenylEthyl, phenyl propyl, benzyl, tolyl, xylyl or naphthyl. An exemplary enforcement sideIn formula, described aryl can be phenyl.
In Chemical formula 1, at least one R can be aryl, for example, and phenyl. Described silicones is passableComprise aryl, make the mol ratio (Ar/Si) of total silicon atom (Si) that aryl (Ar) and described resin comprise largeIn 0.3,0.5 or 0.7. If described mol ratio (Ar/Si) exceedes 0.3, can keep excellent refractive index,Optical property, moisture resistance, weatherability and hardness performance. Not special to the upper limit of described mol ratio (Ar/Si)Restriction for example, can be below 2.0, below 1.5 or below 1.2.
In Chemical formula 1, the molar fraction that a, b, c, d and e are each unit. If (a+b+c+d+e)Summation be 1, a can be 0 to 0.6 or 0 to 0.5, b can be 0 to 0.97 or 0 to 0.8,C can be 0 to 0.8 or 0 to 0.7, d can be 0 to 0.4 or 0 to 0.2,eCan be 0 or positive number.If e is positive number, can improve the function of the metallic in the stabilising membrane of silicones.
Described silicones can be, for example, and crosslinked silicones. Term " crosslinked silicones " can representMust comprise T unit or the Q unit resin as siloxane unit. For example, crosslinked silicones is passableRepresent T unit and Q unit. Therefore when, c is different with d, be 0.
Described silicones can comprise select a kind of in free Chemical formula 2 and 3 siloxane units that represent orMultiple.
[Chemical formula 2]
(R4R5SiO2/2)
[chemical formula 3]
(R6SiO3/2)
In Chemical formula 2 and 3, R4And R5Represent independently alkyl or aryl, R4And R5In at leastOne is aryl, R6For aryl.
The siloxane unit of Chemical formula 2 is the D unit that comprises the aryl being connected at least one silicon atom.For example, the siloxanes of Chemical formula 2 can be the siloxane unit of chemical formula 4 or 5.
[chemical formula 4]
(C6H5)(CH3)SiO2/2
[chemical formula 5]
(C6H5)2SiO2/2
In addition, chemical formula 3 can represent the T unit that comprises the aryl being connected on silicon atom, and exampleAs being the siloxane unit being represented by chemical formula 6.
[chemical formula 6]
(C6H5)SiO3/2
In described silicones, the aryl being connected on all silicon atoms comprising in this resin can wrapBe contained in the siloxane unit of Chemical formula 2 or 3. In addition, in this case, the unit of Chemical formula 2Can be the unit of chemical formula 4 or 5, the unit of chemical formula 3 can be the unit of chemical formula 6.
It is 500 to 100,000 that described silicones can have scope, ideally 1,000 to 50,000 weightAverage molecular weight (Mw). By the molecular weight of the described resin of control described above, using described compositionIn each step, can keep excellent serviceability and processing characteristics, and all right after curing scheduleKeep excellent hardness, photostability and durability. Described weight average molecular weight is for passing through gel permeation chromatographyThe polystyrene standard conversion values of method (GPC).
Described composition can comprise silicones or as the material based on silicon of precursor that can form siliconesMaterial. Term " precursor or the material based on silicon " is the common name that can form all kinds material of silicones, exampleAs, can be addition-curable composition, can condensation or composition that can condensation curing, can ultraviolet rayCuring composition or the composition of peroxide cure. In exemplary embodiment, described precursorCan be, but be not limited to, the composition of addition-curable, can condensation or composition that can condensation curing orUltraviolet solidifiable composition.
The silicon composition of addition-curable can form silicones by hydrosilylation reactions. Can in useIn the situation of the silicon composition of addition curing, the organosilicon chemical combination that comprises the hydrogen atom being connected on silicon atomThe organo-silicon compound that thing and comprising is connected to the thiazolinyl on silicon atom can use catalyst, and (for example platinum class is urgedAgent) solidify, can prepare thus silicones.
In addition, condensation curable or composition that can condensation curing comprise and have hydrolyzable and/or can condensation(Li is as ， – Cl ,-OCH in functional group3、-OC(O)CH3、-O(CH3)2、-OHCOCH3Huo – OCH3)Organosilan or siloxanes. Described organosilan or siloxanes can solidify by hydrolysis and/or condensation reaction,Can prepare thus silicones.
In addition, ultraviolet solidifiable composition can comprise silicon compound, for example, has and can pass throughThe silane of the functional group of polymerizable ultraviolet or siloxanes, described functional group is anti-for hydrolysis and/or condensationShould, for for example, (methyl) acryloyl group or vinyl or its hydrolysate, can prepare silicones thus.Ultraviolet ray can be for the preparation of silicones.
In affiliated field, known multiple material, for example, can be according to the knot of required siliconesThe silicon materials of the addition-curable that structure or an average group accepted way of doing sth are selected, condensation curable or silicon that can condensation curingMaterial or ultraviolet solidifiable silicon materials, and by using the bar of this material for the preparation of siliconesPart or reaction additives. By adopting suitably above-mentioned material, those skilled in the art can form baseIn the material of silicon.
In exemplary embodiment, described precursor can be the composition of condensation curable, comprise byThe compound that chemical formula 7 represents or the compound being represented by chemical formula 8; Or comprise by chemical formula 7 and representCompound and the compound being represented by chemical formula 8.
[chemical formula 7]
Si(R7)(R8)3
[chemical formula 8]
Si(R8)4
In chemical formula 7 or 8, R7For being connected to the substituting group on silicon atom, and represent hydrogen, alkylOr aryl, R8For the functional group of condensation curable.
In chemical formula 7 or 8, R8Be not particularly limited, for example, as long as it can be by condensation reaction (,Collosol and gel condensation reaction) formation siloxane backbone (Si-O-Si-). In exemplary embodiment,R8Can be halogen (for example, Cl) ,-OR9、-OC(=O)R9、-N(R9)2、-N(-C(=O)R9)2Or-SR9。At this, for example, R9Can represent independently hydrogen or alkyl, but be not limited to this.
For example, the organo-metallic compound comprising in described composition or its condensation product can serving as reasonsThe compound that formula 9 represents or its condensation product.
[chemical formula 9]
M(R1)2(R2)n
In chemical formula 9, M is in 3-the 5th family and 12-the 15th family being selected from the periodic table of elementsArbitrary metallic element, R1For being connected to the organo-functional group on M, R2For can condensation functional group, n be0,1 or 2.
In the compound being represented by chemical formula 9, M represents metal, and the oxide of this metal has 1.6Above refractive index, and M can be in 3-the 5th family and 12-the 15th family in the periodic table of elementsArbitrary metallic element. For example, described metal can be the 4th family or the 12nd family in the periodic table of elementsIn metal, or titanium, zirconium or zinc.
In addition, in chemical formula 9, R1Can be for being connected to the organic residue on M. Described organic residueAnd the key between metal can comprise hydrogen bond, ionic bond, covalent bond or coordinate bond, for example, can be for being total toValence link or coordinate bond. For example, described organic residue can be alkoxyl, alkyl oxy alkoxyl, beta-diketon,Beta-diketonate ligand (beta-diketonate) or alkanolamine.
For example, the organic residue being represented by Chemical formula 10 can be used as R1。
[Chemical formula 1 0]
In Chemical formula 10, * represents the key between O and M, and R11Represent hydrogen, alkyl or-OR3。At this, R3For hydrogen or monovalence alkyl.
In Chemical formula 10, the unshared electron pair of the oxygen atom comprising in carbonyl can with chemical formula 9In M form coordinate bond.
R2It can be the residue being represented by Chemical formula 11.
[Chemical formula 1 1]
In Chemical formula 11, * represents the key between O and M, each R12Represent hydrogen, alkyl or aryl,At least one R12Can be hydrogen or alkyl, R13Represent hydrogen or alkyl.
In the residue being represented by Chemical formula 11, for example, at least one R12Can be 2-hydroxyethyl or2-hydroxypropyl, and R12Can be separately form covalent bond or coordinate bond with identical atom, or can be withDifferent atoms forms covalent bond or coordinate bond.
In the organo-metallic compound being represented by chemical formula 9, R2Expression can condensation functional group, n represents0,1 or 2. Functional group that can condensation can comprise can induce the functional group of condensation reaction and by hydrolysisReaction etc. can be converted into the precursor of functional group that can condensation. In organo-metallic compound, R2Pass through waterSeparate the condensation product that reaction and/or condensation reaction can form described compound.
R2Kind be not particularly limited, can be for example hydroxyl or alkoxyl. Represented by chemical formula 9Compound in, for example, R1Can be for alkoxyl, the residue being represented by Chemical formula 10 or by Chemical formula 11The residue representing. In another exemplary embodiment, R1Can be alkoxyl, be shown by Chemical formula 10The residue showing.
The organo-metallic compound being represented by chemical formula 9 can pass through multiple synthetic side well known in the artMethod is synthetic.
When if desired, described composition can comprise the organo-metallic compound that represented by chemical formula 9 or itsCondensation product.
For example, the condensation product of described organo-metallic compound can be represented by Chemical formula 12.
[Chemical formula 1 2]
In Chemical formula 12, M is 3-the 5th family in the periodic table of elements, and in 12-the 15th familyArbitrary metallic element, R1For being connected to the organo-functional group on M, M is as defined in chemical formula 9,M represents more than 2 or 3 to 10 numerical value, R14Represent hydrogen, alkoxyl or monovalence alkyl.
For example, R14Can be alkoxyl or alkyl, for example can be for thering is the alcoxyl of 1 to 8 carbon atomBase or there is the alkyl of 1 to 8 carbon atom.
Use the R of the compound being represented by chemical formula 91Or R2Anti-by multiple hydrolysis well known in the artShould and/or condensation reaction can prepare the compound being represented by Chemical formula 12.
The condensation product (compound for example, being represented by Chemical formula 1 2) of the compound being represented by chemical formula 9Can there is molecular weight or weight average molecular weight below 1,000. Within the scope of this, described condensation product is passableBe dispersed in composition with high concentration, and can form and there is excellent transparency and high refrangible groupCompound or its cured product.
With respect to silicones or its precursor of 100 weight portions, described composition can comprise 10 weight portions extremely800 weight portions represent organo-metallic compound or its condensation product by chemical formula 9. Within the scope of this, canThere is excellent transparency and high refrangible composition or its cured product to provide.
In this manual, unit " weight portion " represents the weight rate of each component.
Described composition can further comprise solvent, can improve thus the serviceability of described compositionAnd processing characteristics. The kind of solvent is not particularly limited, for example can comprise alcohols solvent, glycols andEther solvent, esters solvent, arsol, ketones solvent, ether solvent or comprise two or more moltenThe mixed solvent of agent. The amount of described solvent is not particularly limited, and can suitably select according to serviceability.
In addition, according to the purposes of application, described composition can further comprise certain additive, for example,Dyestuff, surfactant or chelating agent.
The application relates to a kind of electro-optical device, and this electro-optical device comprises substrate and on this substrateThe cured product of the described composition forming.
Described composition can form has excellent transparency and high refrangible cured product, and shouldComposition has excellent heat resistance, light resistance, moisture resistance and weatherability. In curing schedule or solidAfter changing step, can there is not outgas phenomenon. In addition,, in deposition step, film has excellent stablizingProperty, and still less there is outgas phenomenon, make it can be applied to the illuminating part of multiple electro-optical devicePosition or photosensitive position, thus the performance of these devices improved.
Described substrate can be flat screen display, optical pickocff, photon chip or photonic circuit,Light emitting diode (LED), Organic Light Emitting Diode (OLED) or photronic luminous site or photosensitive portionPosition. In addition, described substrate can be the electronics of the multiple film need to high refractiveness and excellent transparencyLuminous or photosensitive position in optics.
The application relates to the preparation method of electro-optical device, and described method comprises: by using solution to be coated withCloth method is coated on described composition on substrate; With the curing composition being coated with.
Can described organo-metallic compound or its condensation product be dispersed in to described composition with high concentrationIn, and can there is not the deteriorated of the transparency that causes due to its gathering. Therefore, described composition can be usedIn preparing electro-optical device by use solution coat method. Therefore, when the large-area electronic light of preparationWhile learning device, can effectively use described composition.
Above-mentioned preparation method comprises by using solution coat method that described composition is coated on substrateStep, can for example pass through dip coated method, knife coating (draw-downcoating), spin-coating method, sprayingMethod or excellent painting method are implemented this step. In this case, be coated with the kind of the substrate of described composition thereonClass is described above.
Above-mentioned preparation method is included in the composition that solidifies coating after application step under suitable conditionStep. In this case, the method for solidifying described composition is not particularly limited, according to the kind of materialClass, can be used the method for for example heating, ultraviolet irradiation or sulfuration.
When if desired, the solvent comprising in processing described composition and remove composition at suitable temperatureCan be prepared afterwards the curing schedule in method.
Beneficial effect
The transparency of the application's compositions display excellence, moisture resistance, heat resistance, resistance to water, weatherability,Light resistance and durability, and can form the high refraction film with high index of refraction. Described composition is addingIn work process or show hardly afterwards outgas, and can solution application coating process, therefore can haveEffect ground is for multiple electro-optical device.
Detailed description of the invention
Hereinafter, will explain in detail described composition with reference to embodiment and comparative example, but described inThe scope of composition is not limited to the following examples.
In an embodiment of the present invention, by method evaluation light transmittance, refractive index and outgas water belowFlat.
1. the measurement of light transmittance
The curable composition of preparing in embodiment and comparative example is coated on glass substrate alsoSolidifying, is the film of 1 μ m thereby form thickness. Check described film by bore hole, based on canonical measure belowIts light transmittance.
<light transmittance evaluation criterion>
O: the situation of not observing mist degree by bore hole
X: the situation of observing mist degree by bore hole
2. the measurement of refractive index
The curable composition of preparing in embodiment and comparative example is coated on substrate also solidChanging, is the film of 1 μ m thereby form thickness. The light that is 450nm to wavelength by UV-VIS spectrometer existsUnder normal temperature, measure the refractive index of described film.
3. the measurement of outgas level
The curable composition of preparing in embodiment and comparative example is coated on substrate also solidChanging, is the film of 1 μ m thereby form thickness. Then, only take out cured layer, and by using thermal analyzerMeasure, cured layer is placed on to 6 hours mass change before and afterwards at 200 DEG C, release thereby evaluateGas performance.
Embodiment 1
Under the existence of acid catalyst by four of the MTMS of 300mmol and 300mmolMethoxy silane sol-gel polymerizations, thus prepare silicones. Then the resin of, being prepared by 2g and 8gPoly-(butyl titanate) (poly (dibutyltitanate)) (degree of polymerization: n=4) be dissolved in the ethylene glycol diethyl ether of 10gIn, thereby prepare curable composition. Then, composition described in spin coating, and the temperature of 200 DEG CSolidify 30 minutes down, thereby form high refractiveness film.
Embodiment 2
Except using the ethyl diacetateization two n-butoxy titanium (titanium of 8gDi-n-butoxide (bis-2,4-pentanedionate)) replace outside poly-(butyl titanate), with embodiment 1 inDescribed identical mode is prepared high refractiveness film.
Embodiment 3
Except using the zirconium tert-butoxide of 8g to replace poly-(butyl titanate), with described in embodiment 1Identical mode is prepared high refractiveness film.
Embodiment 4
Under the existence of acid catalyst by four of the phenyltrimethoxysila,e of 300mmol and 300mmolMethoxy silane sol-gel polymerizations, thus prepare silicones. Then the resin of, being prepared by 2g and 8gPoly-(butyl titanate) that in embodiment 1, use be dissolved in the ethylene glycol diethyl ether of 10g, thereby preparationCurable composition. Then, composition described in spin coating, and solidify 30 minutes at the temperature of 200 DEG C,Thereby form high refractiveness film.
Comparative example 1
Under the existence of acid catalyst by four of the MTMS of 300mmol and 300mmolMethoxy silane sol-gel polymerizations, thus prepare silicones. Then the resin dissolves of, being prepared by 2g existsIn the ethylene glycol diethyl ether of 10g, thereby prepare curable composition. Then, be coated with described composition,And solidify 30 minutes, thereby form film at the temperature of 200 DEG C.
Comparative example 2
Except using the titanium dioxide dispersion soln (solid concentration: 35 % by weight, average grain diameter: 10nm) of 5gReplace outside poly-(butyl titanate), to prepare cured film with the identical mode of describing in embodiment 1.
Comparative example 3
Except using the zirconia dispersion soln (solid concentration: 25 % by weight, average grain diameter: 20nm) of 8gReplace outside poly-(butyl titanate), to prepare cured film with the identical mode of describing in embodiment 1.
The measurement result of the performance of the film of preparing in embodiment and comparative example is listed in the table below in 1.
[table 1]
As the result of listing from table 1 can be found out, have excellent transparent according to the application's compositionDegree, and can form the cured film with high index of refraction. About this point, when using metal oxide grainThe period of the day from 11 p.m. to 1 a.m, is difficult to form the cured film simultaneously with transparency and high index of refraction. Comparative example 2 and 3In, on film, there is very serious mist degree, and serious light scattering, and be therefore difficult to measure foldingPenetrate rate. In addition can find out according in all compositions of the application, for evaluating outgas level,Low the reaching below 0.3% of weight reducing rate.
Claims (15)
1. a high refraction composition, comprises:
There is silicones or its precursor of an average group accepted way of doing sth for Chemical formula 1; With
The condensation product of the compound that represented by chemical formula 9, the compound that should be represented by chemical formula 9 or byThe compound that Chemical formula 12 represents:
[Chemical formula 1]
(R3SiO1/2)a(R2SiO2/2)b(RSiO3/2)c(SiO4/2)d(XO1/2)e
[chemical formula 9]
M(R1)2(R2)n，
Wherein, each R is the substituting group being connected on silicon atom, and represent independently hydrogen, alkyl orAryl; X represents hydrogen atom or alkyl; The summation of a, b, c, d and e is that 1, a 0 to 0.6, b is0 to 0.97, c is 0 to 0.8, d to be 0 to 0.4, e to be 0 or positive number, and the M of chemical formula 9 is for being selected fromMetallic element in 3-the 5th family in the periodic table of elements and the metallic element of 12-the 15th family, chemistryThe R of formula 91For being connected to M organo-functional group upper and that represented by Chemical formula 10 or 11, chemical formula 9R2For functional group that can condensation, the n of chemical formula 9 is 0 to 2:
[Chemical formula 1 0]
Wherein, the mark of Chemical formula 10 " * " represents that O is connected on the M of chemical formula 9, Chemical formula 10R11Represent hydrogen, alkyl or-OR3, wherein R3For hydrogen or monovalence alkyl;
[Chemical formula 1 1]
Wherein, the mark of Chemical formula 11 " * " represents that O is connected on the M of chemical formula 9, at least oneIndividual R12In situation for hydrogen or alkyl, each R of Chemical formula 1112Represent hydrogen, alkyl or aryl; ChemistryThe R of formula 1113Represent hydrogen or alkyl;
[Chemical formula 1 2]
Wherein, the M of Chemical formula 12 is for being selected from the periodic table of elements the 3rd to the 5th family and the 12nd to the 15thMetallic element in the metallic element of family, the R of Chemical formula 121For alkoxyl or alkyl oxy alkoxyl, changeThe m of formula 12 represents more than 2 numerical value, the R of Chemical formula 1214Represent hydrogen, alkoxyl or monovalence hydrocarbonBase.
2. high refraction composition according to claim 1, wherein, the folding before or after solidifyingThe rate of penetrating is more than 1.50.
3. high refraction composition according to claim 1, wherein, described silicones is crosslinked siliconResin.
4. high refraction composition according to claim 1, wherein, described silicones comprises aryl.
5. high refraction composition according to claim 1, wherein, described silicones comprises by chemistryThe siloxane unit that formula 3 or chemical formula 4 represent:
[chemical formula 3]
(R4R5SiO2/2)
[chemical formula 4]
(R6SiO3/2)，
Wherein, at R4And R5In at least one situation that is aryl under, R4And R5Represent independently alkaneBase or aryl; R6For aryl.
6. high refraction composition according to claim 1, wherein, the weight average molecule of described siliconesAmount is in 500 to 100,000 scope.
7. high refraction composition according to claim 1, wherein, described precursor is addition-curableComposition, condensation curable or the composition of composition that can condensation curing, UV curable or canThe composition of peroxide cure.
8. high refraction composition according to claim 1, wherein, the precursor of described silicones comprisesThe compound being represented by chemical formula 8 or the compound being represented by Chemical formula 13:
[chemical formula 8]
Si(R7)(R8)3
[Chemical formula 1 3]
Si(R8)4
Wherein, R7For being connected to the substituting group on silicon atom, and represent hydrogen, alkyl or aryl, R8ForThe functional group of condensation curable.
9. high refraction composition according to claim 1, wherein, described chemical formula 9 or chemical formula12 M is the 4th family in the periodic table of elements or the metal of the 12nd family.
10. high refraction composition according to claim 1, wherein, the change being represented by Chemical formula 12The weight average molecular weight of compound is below 1,000.
11. high refraction compositions according to claim 1, wherein, with respect to 100 weight portionsDescribed silicones or its precursor, the described compound being represented by chemical formula 9, the change being represented by chemical formula 9The content of the condensation product of compound or the compound that represented by Chemical formula 12 is 10 weight portion to 800 weightPart.
12. high refraction compositions according to claim 1, also comprise solvent.
13. 1 kinds of electro-optical devices, comprising:
Substrate; With
The cured product of the composition claimed in claim 1 forming on described substrate.
14. electro-optical devices according to claim 13, wherein, described substrate is flat screenDisplay, optical pickocff, photon chip, photonic circuit, light emitting diode, Organic Light Emitting Diode,Or photronic luminous site or photosensitive position.
Prepare the method for electro-optical device, comprising for 15. 1 kinds: by solution coat method by claim 1Described composition is coated on substrate; With curing described composition.
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| KR10-2011-0059097 | 2011-06-17 | ||
| KR20110059097 | 2011-06-17 | ||
| PCT/KR2012/004819 WO2012173459A2 (en) | 2011-06-17 | 2012-06-18 | Composition having high refraction |
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| EP (1) | EP2722365B1 (en) |
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| JP5667282B1 (en) * | 2013-12-27 | 2015-02-12 | 古河電気工業株式会社 | Filling material for organic electroluminescence device and sealing method of organic electroluminescence device |
| KR102307458B1 (en) * | 2014-10-20 | 2021-09-30 | 삼성전자주식회사 | Color splitter and method for manufacturing the same and image sensor including the same |
| KR101908163B1 (en) | 2014-12-03 | 2018-10-16 | 삼성에스디아이 주식회사 | Composition for window film, flexible window film prepared using the same and flexible display apparatus comprising the same |
| KR101835866B1 (en) | 2014-12-17 | 2018-03-08 | 삼성에스디아이 주식회사 | Composition for window film, flexible window film prepared using the same and flexible display apparatus comprising the same |
| KR101835867B1 (en) | 2014-12-23 | 2018-03-08 | 삼성에스디아이 주식회사 | Composition for window film, flexible window film prepared using the same and flexible display apparatus comprising the same |
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| KR101537144B1 (en) | 2015-07-16 |
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| KR20120139616A (en) | 2012-12-27 |
| EP2722365B1 (en) | 2020-05-13 |
| EP2722365A4 (en) | 2015-01-07 |
| JP5824577B2 (en) | 2015-11-25 |
| US9285507B2 (en) | 2016-03-15 |
| WO2012173459A3 (en) | 2013-03-28 |
| CN103608407A (en) | 2014-02-26 |
| EP2722365A2 (en) | 2014-04-23 |
| WO2012173459A2 (en) | 2012-12-20 |
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